Electrochromic Devices and Compositions Including Anodic Component Anions

ABSTRACT

The present invention relates to electrochromic devices and compositions, in which the anodic component thereof includes an anodic component anion selected from at least one anodic component anion represented by the following Formulas (I) or (II),With reference to Formulas (I) and (II), R1 and R2 are each independently selected from divalent linear or branched alkane linking group. With reference to Formula (II), R3 is selected from fluorine, linear or branched fluorinated alkyl, or linear or branched perfluorinated alkyl. The present invention also relates to salts including an anion represented by Formula (II). The present invention further relates to a neutral compound corresponding to Formula (II), in which hydrogen (H) is bonded to the nitrogen anion.

CROSS-REFERENCE TO RELATED APPLICATION

This application is entitled to and claims priority to U.S. ProvisionalPatent Application No. 63/333,182, filed on Apr. 21, 2022, thedisclosure of which is incorporated herein by reference in its entirety.

FIELD

The present invention relates to electrochromic devices and compositionsthat include anodic component anions, in which an anion is covalentlybonded to the anodic component or group.

BACKGROUND

Electrochromism involves a reversible change in a material's visiblecolor and/or transmittance of visible light with the application of anelectrical potential. The change in color and/or transmittance typicallyinvolves alternately cycled oxidized and reduced charge states.Generally, a material that generates a color while undergoing reductionis referred to as a cathodically-coloring electrochromic material; and amaterial that generates color while undergoing oxidation is referred toas an anodically-coloring electrochromic material.

Electrochromic devices typically include opposed electrodes (e.g., ananode and a cathode) having interposed there-between an electrochromiclayer that is solution or gel-based. The kinetics of such electrochromicdevices is typically governed primarily by mass transport of cathodiccomponents and anodic components across and through the electrochromiclayer. For purposes of charge conversion, the electrical currents ofboth electrodes are necessarily equal. If one of the components(cathodic or anodic component) moves or is transported more slowlythrough or across the electrochromic layer, typically a higherconcentration of that component is required, and more particularly, ahigher concentration gradient of the slower moving/transported componentat the electrode interface (a higher interfacial concentration) isrequired to equalize the diffusion flux and maintain a given current.Adjusting and/or maintaining a higher concentration of the componenthaving reduced mass transport can require additional preparation and/ormanufacturing steps, and can result in inadvertent formulation errors.Mass transport imbalances can, in some instances, result in reduceddurability of the electrochromic device, in particular if the slowermass transported active component is subject to over-oxidization orover-reduction at a particular electrode.

Factors that contribute to reduced mass transport of a component, andcorrespondingly mass transport imbalance as between the components,include, but are not limited to, reduced solubility of that component inthe electrochromic layer and/or lack of a charge associated therewith.With some electrochromic devices, the cathodic component has a positivecharge and has associated therewith counter-anions, while the anodiccomponent has no charge associated therewith. The lack of chargeassociated with the anodic component can contribute to an undesirablemass transport imbalance relative to the cathodic component.

It would be desirable to develop new electrochromic devices andcompositions in which the active components thereof, and in particular,the cathodic and anodic components, provide improved mass transportbalance. It would be further desirable that such newly developedelectrochromic devices and compositions provide, or otherwise haveassociated therewith, improved durability, reduced costs of manufactureand/or operation, and/or improved efficiency of operation.

SUMMARY

In accordance with the present invention, there is provided anelectrochromic device comprising: (a) a first substrate having a surfacecomprising a first transparent electrode layer; (b) a second substratehaving a surface comprising a second transparent conductive electrodelayer, wherein said first transparent electrode layer and said secondtransparent electrode layer are in opposing spaced opposition relativeto each other; and (c) an electrochromic layer interposed between saidfirst transparent electrically conductive electrode layer and saidsecond transparent electrically conductive electrode layer. Theelectrochromic layer comprises: (i) a cathodic component; and (ii) ananodic component comprising an anodic component anion selected from atleast one anodic component anion represented by the following Formula(I) or Formula (II),

With reference to Formula (I), R¹ is selected from divalent linear orbranched alkane linking group. With reference to Formula (II), R² isselected from divalent linear or branched alkane linking group, and R³is selected from fluorine, linear or branched fluorinated alkyl, orlinear or branched perfluorinated alkyl. The electrochromic layerfurther comprises: (iii) an optional electrolyte; and (iv) a polymermatrix.

In accordance with the present invention, there is further provided anelectrochromic composition comprising: (i) a cathodic component; (ii) ananodic component comprising an anodic component anion selected from atleast one anodic component anion represented by Formula (I) or Formula(II), as described above; (iii) an optional electrolyte; (iv) apolymeric thickener; and (v) a solvent.

In further accordance with the present invention, there is provided acompound represented by the following Formula (IIa),

With reference to Formula (IIa), R² is selected from divalent linear orbranched alkane linking group; and R³ is selected from fluorine, linearor branched fluorinated alkyl, or linear or branched perfluorinatedalkyl.

In accordance with the present invention, there is additionally provideda salt comprising an anion represented by the following Formula (II),

With reference to Formula (II), R² is selected from divalent linear orbranched alkane linking group; and R³ is selected from fluorine, linearor branched fluorinated alkyl, or linear or branched perfluorinatedalkyl.

The features that characterize the present invention are pointed outwith particularity in the claims, which are annexed to and form a partof this disclosure. These and other features of the invention, itsoperating advantages and the specific objects obtained by its use willbe more fully understood from the following detailed description inwhich non-limiting embodiments of the invention are illustrated anddescribed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representative side elevational sectional view of anelectrochromic device according to the present invention; and

FIG. 2 is a graphical representation of plots of % transmission vs.wavelength obtained from an electrochromic device according to thepresent invention in the activated (dark) and unactivated (clear)states, as described in the Examples herein.

In FIGS. 1 and 2 like characters refer to the same components and/orelements, as the case may be, unless otherwise stated.

DETAILED DESCRIPTION

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all values, and subranges orsubratios subsumed therein. For example, a stated range or ratio of “1to 10” should be considered to include any and all values there-between(such as, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), and subranges between (andinclusive of) the minimum value of 1 and the maximum value of 10; thatis, all subranges or subratios beginning with a minimum value of 1 ormore and ending with a maximum value of 10 or less, such as but notlimited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein, unless otherwise indicated, left-to-rightrepresentations of linking groups, such as divalent linking groups, areinclusive of other appropriate orientations, such as, but not limitedto, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup

or equivalently —C(O)O—, is inclusive of the right-to-leftrepresentation thereof,

or equivalently —O(O)C— or —OC(O)—.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asmodified in all instances by the term “about.”

As used herein, molecular weight values of polymers, such as weightaverage molecular weights (Mw) and number average molecular weights(Mn), are determined by gel permeation chromatography using appropriatestandards, such as polystyrene standards.

As used herein, polydispersity index (PDI) values represent a ratio ofthe weight average molecular weight (Mw) to the number average molecularweight (Mn) of the polymer (i.e., Mw/Mn).

As used herein, the term “polymer” means homopolymers (e.g., preparedfrom a single monomer species), copolymers (e.g., prepared from at leasttwo monomer species), and graft polymers.

As used herein, the term “(meth)acrylate” and similar terms, such as“(meth)acrylic acid ester” means methacrylates and/or acrylates. As usedherein, the term “(meth)acrylic acid” means methacrylic acid and/oracrylic acid.

As used herein, the term “electrochromic” and similar terms, such as“electrochromic compound” means having an absorption spectrum for atleast visible radiation that varies in response to the application of anelectric potential. Further, as used herein the term “electrochromicmaterial” means any substance that is adapted to display electrochromicproperties (such as, adapted to have an absorption spectrum for at leastvisible radiation that varies in response to an applied electricpotential) and which includes at least one electrochromic compound.

As used herein, the term “electric potential” and related terms such as“electrical potential” means an electric potential that is capable ofcausing a response in a material, such as, but not limited to,transforming an electrochromic material from one form or state toanother, as will be discussed in further detail herein.

As used herein to modify the term “state,” the terms “first” and“second” are not intended to refer to any particular order orchronology, but instead refer to two different conditions or properties.For purposes of non-limiting illustration, the first state and thesecond state of an electrochromic compound, such as ananodically-coloring electrochromic compound, can differ with respect toat least one optical property, such as but not limited to the absorptionof visible and/or UV radiation. Thus, according to various non-limitingembodiments disclosed herein, the anodically-coloring electrochromiccompounds of the present invention can have a different absorptionspectrum in each of the first and second state. For example, while notlimiting herein, an anodically-coloring electrochromic compound can beclear in the first state and colored in the second state. Alternatively,an anodically-coloring electrochromic compound can have a first color inthe first state and a second color in the second state.

As used herein the term “display” means the visible or machine-readablerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements include screens,monitors, and security elements, such as security marks.

As used herein the term “window” means an aperture adapted to permit thetransmission of radiation there-through. Non-limiting examples ofwindows include automotive and aircraft transparencies, windshields,filters, shutters, and optical switches.

As used herein the term “mirror” means a surface that specularlyreflects a large fraction of incident light.

As used herein, spatial or directional terms, such as “left”, “right”,“inner”, “outer”, “above”, “below”, and the like, relate to theinvention as it is depicted in the drawing figures. It is to beunderstood, however, that the invention can assume various alternativeorientations and, accordingly, such terms are not to be considered aslimiting.

As used herein, the terms “formed over,” “deposited over,” “providedover,” “applied over,” residing over,” or “positioned over,” meanformed, deposited, provided, applied, residing, or positioned on but notnecessarily in direct (or abutting) contact with the underlying element,or surface of the underlying element. For example, a layer “positionedover” a substrate does not preclude the presence of one or more otherlayers, coatings, or films of the same or different composition locatedbetween the positioned or formed layer and the substrate.

As used herein, the terms “interposed” and “interposed between,” meanresiding or positioned between, but not necessarily in direct (orabutting) contact with overlying and/or underlying elements, or surfacesthereof. For example, a layer “interposed between” a first substrate anda second substrate does not preclude the presence of one or more otherlayers, coatings, or films of the same or different composition locatedbetween the interposed layer and the first and/or second substrates.

All documents, such as but not limited to issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

As used herein, recitations of “linear or branched” groups, such aslinear or branched alkyl, are herein understood to include: a methylenegroup or a methyl group; groups that are linear, such as linear C₂-C₂₀alkyl groups; and groups that are appropriately branched, such asbranched C₃-C₂₀ alkyl groups.

The term “alkyl” as used herein means linear or branched, cyclic oracyclic C₁-C₂₅ alkyl. Linear or branched alkyl can include C₁-C₂₅ alkyl,such as C₁-C₂₀ alkyl, such as C₂-C₁₀ alkyl, such as C₁-C₁₂ alkyl, suchas C₁-C₆ alkyl. Examples of alkyl groups from which the various alkylgroups of the present invention can be selected from, include, but arenot limited to, those recited further herein. Alkyl groups can include“cycloalkyl” groups. The term “cycloalkyl” as used herein means groupsthat are appropriately cyclic, such as, but not limited to, C₃-C₁₂cycloalkyl (including, but not limited to, cyclic C₃-C₁₀ alkyl, orcyclic C₅-C₇ alkyl) groups. Examples of cycloalkyl groups include, butare not limited to, those recited further herein. The term “cycloalkyl”as used herein also includes: bridged ring polycycloalkyl groups (orbridged ring polycyclic alkyl groups), such as, but not limited to,bicyclo[2.2.1]heptyl (or norbornyl) and bicyclo[2.2.2]octyl; and fusedring polycycloalkyl groups (or fused ring polycyclic alkyl groups), suchas, but not limited to, octahydro-1H-indenyl, and decahydronaphthalenyl.

The term “heterocycloalkyl” as used herein means groups that areappropriately cyclic, such as, but not limited to, C₂-C₁₂heterocycloalkyl groups, such as C₂-C₁₀ heterocycloalkyl groups, such asC₅-C₇ heterocycloalkyl groups, and which have at least one hetero atomin the cyclic ring, such as, but not limited to, O, S, N, P, andcombinations thereof. Examples of heterocycloalkyl groups include, butare not limited to, imidazolyl, tetrahydrofuranyl, tetrahydropyranyl andpiperidinyl. The term “heterocycloalkyl” as used herein also includes:bridged ring polycyclic heterocycloalkyl groups, such as, but notlimited to, 7-oxabicyclo[2.2.1]heptanyl; and fused ring polycyclicheterocycloalkyl groups, such as, but not limited to,octahydrocyclopenta[b]pyranyl, and octahydro-1H-isochromenyl.

The descriptions, classes, and examples provided herein with regard toalkyl groups, cycloalkyl groups, heterocycloalkyl groups, haloalkylgroups, and the like, are also applicable to alkane groups, cycloalkanegroups, heterocycloalkane groups, haloalkane groups, etc., such as, butnot limited to, polyvalent alkane groups, such as polyvalent alkanelinking groups, such as divalent alkane linking groups.

As used herein, the term “aryl” and related terms, such as “aryl group”,means an aromatic cyclic monovalent hydrocarbon radical. As used herein,the term “aromatic” and related terms, such as “aromatic group,” means acyclic conjugated hydrocarbon having stability (due to delocalization ofpi-electrons) that is significantly greater than that of a hypotheticallocalized structure. Examples of aryl groups include C₆-C₁₄ aryl groups,such as, but not limited to, phenyl, naphthyl, phenanthryl, andanthracenyl.

The term “heteroaryl”, as used herein, includes, but is not limited to,C₃-C₁₈ heteroaryl, such as, but not limited to, C₃-C₁₀ heteroaryl(including fused ring polycyclic heteroaryl groups) and means an arylgroup having at least one hetero atom in the aromatic ring, or in atleast one aromatic ring in the case of a fused ring polycyclicheteroaryl group. Examples of heteroaryl groups include, but are notlimited to, furanyl, pyranyl, pyridinyl, quinolinyl, isoquinolinyl, andpyrimidinyl.

Representative alkyl groups include, but are not limited to, methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representativealkenyl groups include, but are not limited to, vinyl, allyl, andpropenyl. Representative alkynyl groups include, but are not limited to,ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl.Representative cycloalkyl groups include, but are not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

The term “nitrogen-containing heterocycle,” such as “nitrogen-containinghererocycle group” or nitrogen-containing heterocycle substituent,” asused herein, includes, but is not limited to, a nitrogen-containing ringin which the nitrogen-containing ring is bonded through a ring nitrogen.Examples of nitrogen-containing heterocycles include, but are notlimited to, aliphatic cyclic aminos (or cycloaliphatic aminos), such asmorpholino, piperidino, pyrrolidino, and decahydroisoquinolino; andheteroaromatics, such as imidazole, pyrrole, indole, and carbazole.

As used herein, recitations of “substituted” group, means a groupincluding, but not limited to, alkyl group, cycloalkyl group,heterocycloalkyl group, aryl group, and/or heteroaryl group, in which atleast one hydrogen thereof has been replaced or substituted with a groupor “substituent” that is other than hydrogen, such as, but not limitedto: alkoxy groups; halo groups (e.g., F, Cl, I, and Br); hydroxylgroups; thiol groups; alkylthio groups; arylthio groups; ketone groups;aldehyde groups; carboxylic ester groups; carboxylic acid groups;phosphoric acid groups; phosphoric acid ester groups; sulfonic acidgroups; sulfonic acid ester groups; nitro groups; cyano groups; alkylgroups; alkenyl groups; alkynyl groups; haloalkyl groups; perhaloalkylgroups; heterocycloalkyl groups; aryl groups (including alkaryl groups,including hydroxyl substituted aryl, such as phenol, and includingpoly-fused-ring aryl); aralkyl groups; heteroaryl groups (includingpoly-fused-ring heteroaryl groups); amino groups, such as—N(R^(11′))(R^(12′)) where R^(11′) and R^(12′) are each independentlyselected from, for example, hydrogen, alkyl, heterocycloalkyl, aryl, orheteroaryl; carboxylate groups; siloxane groups; alkoxysilane groups;polysiloxane groups; amide groups; carbamate groups; carbonate groups;urea groups; trialkylsilyl groups; nitrogen-containing heterocycles; orcombinations thereof, including those classes and examples as describedfurther herein. In accordance with some embodiments of the presentinvention, the substituents of a substituted group are more particularlyrecited.

As used herein, the term “halo” and related terms, such as “halo group,”“halo substituent,” “halogen group,” and “halogen substituent,” means asingle bonded halogen group, such as —F, —Cl, —Br, and —I.

As used herein, recitations of “halo substituted” and related terms(such as, but not limited to, haloalkyl groups, haloalkenyl groups,haloalkynyl groups, haloaryl groups, and halo-heteroaryl groups) means agroup in which at least one, and up to and including all of theavailable hydrogen groups thereof is substituted with a halo group, suchas, but not limited to F, Cl or Br. The term “halo-substituted” isinclusive of “perhalo-substituted.” As used herein, the termperhalo-substituted group and related terms (such as, but not limitedto, perhaloalkyl groups, perhaloalkenyl groups, perhaloalkynyl groups,perhaloaryl groups or perhalo-heteroaryl groups) means a group in whichall of the available hydrogen groups thereof are substituted with a halogroup. For purposes of non-limiting illustration: perhalomethyl is —CX₃;and perhalophenyl is —C₆X₅, where X represents one or more halo groups,such as, but not limited to F, Cl, Br, or I.

As used herein, “at least one of” is synonymous with “one or more of,”whether the elements are listed conjunctively or disjunctively. Forexample, the phrases “at least one of A, B, and C” and “at least one ofA, B, or C” each mean any one of A, B, or C, or any combination of anytwo or more of A, B, or C. For example, A alone; or B alone; or C alone;or A and B; or A and C; or B and C; or all of A, B, and C.

As used herein, “selected from” is synonymous with “chosen from” whetherthe elements are listed conjunctively or disjunctively. Further, thephrases “selected from A, B, and C” and “selected from A, B, or C” eachmean any one of A, B, or C, or any combination of any two or more of A,B, or C. For example, A alone; or B alone; or C alone; or A and B; or Aand C; or B and C; or all of A, B, and C.

The discussion of the present invention herein may describe certainfeatures as being “particularly” or “preferably” within certainlimitations (e.g., “preferably,” “more preferably,” or “even morepreferably,” within certain limitations). It is to be understood thatthe invention is not limited to or by such particular or preferredlimitations, but encompasses the entire scope of the disclosure.

As used herein, and in accordance with some embodiments, the term“ketone” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “ketone group” and “ketone substituent,” includesa material represented by —C(O)R, where R is selected from those groupsas described below, other than hydrogen.

As used herein, and in accordance with some embodiments, the term“carboxylic acid” such as with regard to groups, and substituents ofvarious groups, of the compounds and components of the presentinvention, and related terms, such as “carboxylic acid group” and“carboxylic acid substituent” includes a material represented by—C(O)OH.

As used herein, and in accordance with some embodiments, the term“ester” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “ester group” and “ester substituent” means acarboxylic acid ester group represented by —C(O)OR, where R is selectedfrom those groups as described below, other than hydrogen.

As used herein, and in accordance with some embodiments, the term“carboxylate” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “carboxylate group” and “carboxylatesubstituent,” includes a material represented by —OC(O)R, where R isselected from those groups as described below.

As used herein, and in accordance with some embodiments, the term“amide” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “amide group” and “amide substituent” includes amaterial represented by —C(O)N(R)(R) or —N(R)C(O)R, where each R isindependently selected from those groups as described below.

As used herein, and in accordance with some embodiments, the term“carbonate” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “carbonate group” and “carbonate substituent”includes a material represented by —OC(O)OR, where R is selected fromthose groups as described below, other than hydrogen.

As used herein, and in accordance with some embodiments, the term“carbamate” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “carbamate group” and “carbamate substituent”includes a material represented by —OC(O)N(R)(H) or —N(H)C(O)OR, where Rin each case is independently selected from those groups as describedbelow, other than hydrogen.

As used herein, and in accordance with some embodiments, the term “urea”such as with regard to groups, and substituents of various groups, ofthe compounds and components of the present invention, and relatedterms, such as “urea group” and “urea substituent” includes a materialrepresented by —N(R)C(O)N(R)(R), where each R is independently selectedfrom those groups as described below.

As used herein, and in accordance with some embodiments, the term“siloxy” such as with regard to groups, and substituents of variousgroups, of the compounds and components of the present invention, andrelated terms, such as “siloxy group” and “siloxy substituent” includesa material represented by —O—Si(R)₃ where each R is independentlyselected from those groups as described below, other than hydrogen.

As used herein, and in accordance with some embodiments, the term“alkoxysilane” such as with regard to groups, and substituents ofvarious groups, of the compounds and components of the presentinvention, and related terms, such as “alkoxysilane group” andalkoxysilane substituent” includes a material represented by—Si(OR″)_(w)(R)_(t), where w is 1 to 3 and t is 0 to 2, provided the sumof w and t is 3; R″ for each w is independently selected from alkyl; andR for each t is independently selected from those groups as describedbelow, other than hydrogen.

As used herein, and in accordance with some embodiments, the term“polysiloxane” such as with regard to groups, and substituents ofvarious groups, of the compounds and components of the presentinvention, and related terms, such as “polysiloxane group” and“polysiloxane substituent”, includes a material represented by thefollowing Formula (A):

With reference to Formula (A): t′ is greater than or equal to 2, such asfrom 2 to 200; R^(f) and R^(g) for each t′ are each independentlyselected from a group R as described below, other than hydrogen; andR^(h) is independently a group R as described below.

Unless otherwise stated, each R group of each of the above describedketone, ester (carboxylic acid ester), carboxylate, amide, carbonate,carbamate, urea, siloxane, alkoxysilane groups, and polysiloxane groups,is in each case independently selected from hydrogen, alkyl, haloalkyl,perhaloalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, andcombinations thereof (including those classes and examples thereof asrecited previously herein).

Reference herein to counter-ions (such as counter-cations and/orcounter-anions) of a component, with some embodiments, means thecounter-ions of the component when it is prepared separately from and/orprior to combining with the electrochromic layer and/or electrochromiccomposition of the present invention.

In accordance with the present invention, the electrochromic material(of the electrochromic layer of the electrochromic device) includes ananodic component, where the anodic component includes an anodiccomponent anion that is selected from at least one anodic componentanion represented by Formula (I) or Formula (II), as provided above. Theanodic component anion can be described as including an anodic portion(group or moiety), such as a (10H-phenothiazin-10-yl) moiety, and ananion that is covalently bonded to the anodic moiety, such as asulfonate anion or a triflamide anion. With some further embodiments,the anion of the anodic component anion is covalently bonded to theanodic group or moiety by a divalent linear or branched alkane linkinggroup. With some further embodiments, the anodic component anion is ananodically-coloring electrochromic compound or group having an anioncovalently bonded thereto.

In accordance with some embodiments of the present invention, and withreference to the anodic component anion represented by Formula (I), R¹is selected from divalent linear or branched C₁-C₁₀ alkane linkinggroup.

With some embodiments, and with reference to the anodic component anionrepresented by Formula (II), R² is selected from divalent linear orbranched C₁-C₁₀ alkane linking group; and R₃ is selected from fluorine,linear or branched C₁-C₁₀ fluorinated alkyl, or linear or branchedC₁-C₁₀ perfluorinated alkyl.

With reference to the anodic component anion represented by Formula (I),and in accordance with some embodiments, R¹ is selected from divalentlinear or branched C₁-C₅ alkyl. With some embodiments, R¹ is selectedfrom divalent methane, divalent ethane, divalent linear or branchedpropane, divalent linear or branched butane, and divalent linear orbranched pentane.

With reference to the anodic component anion represented by Formula(II), and in accordance with some embodiments, R² is selected fromdivalent linear or branched C₁-C₅ alkane linking group; and R³ isselected from linear or branched C₁-C₅ perfluorinated alkyl. With someembodiments, R² is selected from divalent methane, divalent ethane,divalent linear or branched propane, divalent linear or branched butane,and divalent linear or branched pentane. With some further embodiments,R³ is selected from fluorinated or perfluorinated versions orderivatives of methyl, ethyl, linear or branched propyl, linear orbranched butyl, and linear or branched pentyl.

With some embodiments of the present invention, anodic component anions(having anions covalently bonded thereto), such as represented byFormula (I) and Formula (II), can be prepared in accordance thenon-limiting synthetic descriptions provided in the examples furtherherein.

In accordance with some further embodiments, the anodic component, whichincludes the anodic component anion, further includes a counter-cation.Classes and examples of cations from which each counter-cation can beindependently selected from include, but are not limited to: alkalimetal cations, such as lithium cation (Li⁺), sodium cation (Na⁺), andpotassium cation (K⁺); alkaline earth metal cations, such as Mg²⁺, Ca²⁺,and Ba²⁺; optionally substituted nitrogen-containing aliphaticheterocycle ammonium cations, such as, optionally substitutedN,N-disubstituted pyrrolidinium cations, optionally substitutedN,N-disubstituted piperidinium cations, and optionally substitutedN,N-disubstituted morpholinium cations; optionally substitutednitrogen-containing aromatic heterocycle ammonium cations such as,optionally substituted N-substituted pyridinium cations, optionallysubstituted N-substituted quinolinium cations, and optionallysubstituted N-substituted isoquinolinium cations; and tetrasubstitutedammonium cations, described in further detail below. The optionalsubstituents of the classes and examples of ammonium cations can beselected from those classes and examples of substituents recitedpreviously herein, such as, but not limited to, linear or branched alkylgroups, cycloalkyl groups, and aryl groups. The N-substituted andN,N-disubstituted groups of the ammonium cations can be selected fromthose classes and examples of substituents recited previously herein,such as, but not limited to, linear or branched alkyl groups, cycloalkylgroups, and aryl groups.

With some embodiments, the counter-cation of the anodic component is amono-cation. In accordance with some further embodiments, thecounter-cation of the anodic component is selected from tetrasubstitutedammonium cations represented by the following Formula (B),

With reference to Formula (B), R^(a), R^(b), R^(c), and R^(d) are eachindependently selected from linear or branched alkyl, unsubstitutedcycloalkyl, substituted cycloalkyl, unsubstituted aryl, and substitutedaryl. With further reference to Formula (B), R^(a), R^(b), R^(c), andR^(d) are each independently selected from linear or branched C₁-C₁₀alkyl, unsubstituted C₃-C₇ cycloalkyl, substituted C₃-C₇ cycloalkyl,unsubstituted phenyl, and substituted phenyl. The substituents of thesubstituted cycloalkyl and substituted phenyl groups can in each case beindependently selected from those substituents as recited previouslyherein, such as, but not limited to linear or branched alkyl groups,cycloalkyl groups, and aryl groups.

With some embodiments, and with reference to Formula (B), each of R^(a),R^(b), R^(c), and R^(d) is independently selected from linear orbranched alkyl. With some further embodiments, each of R^(a), R^(b),R^(c), and R^(d) of Formula (B) is independently selected from linear orbranched C₁-C₁₀ alkyl.

Each counter-cation, of the anodic component, is independently selectedfrom tetra(linear or branched alkyl) ammonium cation, with someembodiments. Each counter-cation, of the anodic component, isindependently selected from tetra(linear or branched C₁-C₁₀ alkyl)ammonium cation, with some further embodiments.

The anodic component, with some embodiments, is composed of, orotherwise consists of: an anodic component anion selected from at leastone anodic component anion represented by Formula (I) or Formula (II);and a counter-cation, where the anodic component has an equal number ofanions and counter-cations, and correspondingly a neutral charge.

The anodic component anion, with some embodiments, is present in theelectrochromic layer in an amount of 0.25 percent by weight to 6.25percent by weight, or from 0.5 percent by weight to 5 percent by weight,or from 1 percent by weight to 3 percent by weight, the percent weightsin each case being based on the total weight of the electrochromiclayer.

In accordance with some embodiments, in addition to the anodic componentanion having an anion covalently bonded thereto, such as represented byFormula (I) and/or Formula (II), the anodic component of theelectrochromic layer includes one or more further anodic electrochromiccompounds, such as, but not limited to: ferrocene and/or ferrocenederivatives (in which at least one cyclopentadienyl ring thereof issubstituted with at least one substituent, including those substituentsrecited previously herein); 5,10-dihydro-5,10-di(linear or branchedC₁-C₁₀ alkyl)phenazine, such as 5,10-dihydro-5,10-dimethylphenazine;N-substitutedphenoxazine, such as N-phenylphenoxazine; and combinationsthereof. With some embodiments, the further anodic electrochromiccomponent is present in an amount of 1 percent by weight to 50 percentby weight, of from 1 percent by weight to 25 percent by weight, or from1 percent by weight to 10 percent by weight, or from 1 percent by weightto 5 percent by weight, the percent weights each being based on thetotal weight of the anodic component anion and the further anodicelectrochromic component. In accordance with some embodiments, when afurther anodic component in present (in addition to the anodic componentanion having an anion covalently bonded thereto) a further cathodiccomponent (or further appropriate amount of cathodic component) can alsobe present. The further cathodic component, with some embodiments,comprises one or more cathodic components represented by Formulas (III)and/or (IV).

The cathodic component of the electrochromic layer of the electrochromicdevice, with some embodiments, includes at least one of a1,1′-disubstituted-4,4′-dipyridinium cation represented by the followingFormula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented bythe following Formula (VI):

With reference to Formula (III), R⁴ and R⁵ are each independentlyselected from linear or branched C₁-C₁₀ alkyl, unsubstituted C₃-C₇cycloalkyl, substituted C₃-C₇ cyloalkyl, unsubstituted aryl, andsubstituted aryl.

With reference to Formula (IV), and in accordance with some embodiments,R⁶ and R⁸ are each independently selected from linear or branched C₁-C₁₀alkyl, unsubstituted C₃-C₇ cycloalkyl, substituted C₃-C₇ cyloalkyl,unsubstituted aryl, and substituted aryl, and R⁷ is selected fromdivalent linear or branched C₁-C₁₀ alkane linking group.

The aryl groups of the unsubstituted aryl groups and substituted arylgroups, from which R⁴ and R⁵ of Formula (III), and R⁶ and R⁸ of Formula(IV), can each be independently selected, include those aryl groups asrecited previously herein, such as, but not limited to, phenyl,naphthyl, phenanthryl, and anthracenyl. The cycloalkyl groups of theunsubstituted cycloalkyl groups and substituted cycloalkyl groups, fromwhich R⁴ and R⁵ of Formula (III), and R⁶ and R⁸ of Formula (IV), caneach be independently selected, include those cycloalkyl groups asrecited previously herein, such as, but not limited to, cyclopentyl,cyclohexyl, and cycloheptyl.

The substituents of the substituted cycloalkyl and substituted arylgroups, from which R⁴ and R⁵ of Formula (III), and R⁶ and R⁸ of Formula(IV), can each be independently selected, include those substituents asrecited previously herein. With some embodiments, each substituent ofthe substituted cycloalkyl and substituted aryl groups, from which R⁴and R⁵ of Formula (III), and R⁶ and R⁸ of Formula (IV), can each beindependently selected, are each independently selected from: alkoxygroups; halo groups (e.g., F, Cl, I, and Br); hydroxyl groups; thiolgroups; alkylthio groups; arylthio groups; ketone groups; aldehydegroups; haloalkyl groups; perhaloalkyl groups; heterocycloalkyl groups;aryl groups; aralkyl groups (such as, benzyl groups); heteroaryl groups;and amino groups.

The linear or branched alkyl groups from which R⁴ and R⁵ of Formula(III), and from which R⁶ and R⁸ of Formula (IV), can each beindependently selected, include those classes and examples of alkylgroups as recited previously herein, such as, but not limited to,methyl, ethyl, linear or branched propyl, linear or branched butyl,linear or branched pentyl, linear or branched hexyl, and linear orbranched heptyl.

With further reference to Formula (III), and in accordance with someembodiments of the present invention, R⁴ and R⁵ are each independentlyselected from linear or branched C₁-C₄ alkyl, unsubstituted phenyl, andsubstituted phenyl.

With further reference to Formula (IV), and in accordance with someembodiments of the present invention, R⁶ and R⁸ are each independentlyselected from linear or branched C₁-C₄ alkyl, unsubstituted phenyl, andsubstituted phenyl, and R⁷ is selected from divalent linear or branchedC₁-C⁸ alkane linking group. With some further embodiments, R⁷ of Formula(IV) is a divalent linear or branched C₁-C₅ alkane linking group, suchas a divalent linear or branched C₃-C₅ alkane linking group.

In accordance with some embodiments of the present invention, thecathodic component further includes counter-anions. With some furtherembodiments, the cathodic component includes an equal number of cationsand counter-anions (or anions), and correspondingly the cathodiccomponent has a net neutral charge. Each counter-anion of the cathodiccomponent, with some embodiments, is independently selected from thegroup consisting of BF₄ ⁻, PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻,(CF₃SO₂)₃C⁻, or B(phenyl)₄ ⁻. With some embodiments, the counter-anionsof the cathodic component do not include and are not selected fromanodic component anions, such as represented by Formulas (I) and (II).

In accordance with some embodiments of the present invention, thecathodic component is present in the electrochromic layer in an amountof from 0.25 percent by weight to 6.25 percent by weight, or from 0.5percent by weight to 5 percent by weight, or from 1 percent by weight to3 percent by weight, the percent weights in each case being based on thetotal weight of the electrochromic layer.

With some embodiments of the present invention, the electrochromic layerof the electrochromic device of the present invention, includes anelectrolyte. The electrolyte includes, with some embodiments, at leastone electrolyte anion and at least one electrolyte cation. Theelectrolyte of the electrochromic layer includes, with some embodiments,an equal number of electrolyte anions and electrolyte cations, andcorrespondingly has a net neutral charge.

With some embodiments, the electrolyte of the electrochromic layerincludes at least one electrolyte anion, where each electrolyte anion isindependently selected from chloride, hexafluorophosphate, andbis(perfluoro(linear or branched C₁-C₆ alkysulfonyl)imide. With somefurther embodiments, the electrolyte of the electrochromic layerincludes at least one electrolyte cation, where each electrolyte cationis independently selected from: sodium; potassium; lithium; ammoniumcations, such as, tetra(linear or branched C₁-C₆)ammonium, and tri(C₅-C₈cycloalkyl)-(linear or branched C₁-C₆ alkyl)ammonium; 1-(linear orbranched C₁-C₆ alkyl)-3-(linear or branched C₁-C₆ alkyl)imidazolium;1-(linear or branched C₁-C₆ alkyl)-1-(linear or branched C₁-C₆alkyl)pyrrolidinium; 1-(linear or branched C₁-C₆ alkyl)-1-(linear orbranched C₁-C₆ alkyl)piperidinium; or phosphonium cations, such as, butnot limited to tetra(linear or branched C₁-C₆ alkyl)phosphonium, ortri(C₅-C₈ cycloalkyl)-(linear or branched C₁-C₆ alkyl)phosphonium.

The electrolyte of the electrochromic layer, with some embodimentsincludes: at least one electrolyte anion, where each electrolyte anionis independently selected from bis(perfluoro(linear or branched C₁-C₆alkysulfonyl)imide; and at least one electrolyte cation, wherein eachelectrolyte cation is independently selected from 1-(linear or branchedC₁-C₆ alkyl)-3-(linear or branched C₁-C₆ alkyl)imidazolium, 1-(linear orbranched C₁-C₆ alkyl)-1-(linear or branched C₁-C₆ alkyl)pyrrolidinium,or 1-(linear or branched C₁-C₆ alkyl)-1-(linear or branched C₁-C₆alkyl)piperidinium.

The electrolyte of the electrochromic layer, with some furtherembodiments includes: at least one electrolyte anion, where eachelectrolyte anion is bis(trifluromethylsulfonyl)imide; and at least oneelectrolyte cation, where each electrolyte cation is independentlyselected from 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium,1-methyl-1-butylpyrrolidinium, and 1-methyl-1-propylpiperidinium.

The electrolyte, with some embodiments, is present in the electrochromiclayer in an amount of from 1 percent by weight to 75 percent by weight,or from 5 percent by weight to 50 percent by weight, or from 10 percentby weight to 30 percent by weight, the percent weights in each casebeing based on the total weight of the electrochromic layer.

In accordance with some further embodiments, the electrochromic layer ofthe present invention includes a solvent. With some additionalembodiments, the solvent is present, in the electrochromic layer,alternatively to or in addition to the electrolyte. The solvent can,with some embodiments, include at least one of ethylene carbonate,propylene carbonate, gamma-butyrolactone, gamma-valerolactone,N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters ofpolyethylene glycol, sulfolane, alpha, omega-(C₂-C₈)dinitriles, ordi(linear or branched C₁-C₈)acetamides. While not intending to be boundby any theory, and in accordance with some embodiments, it is believedthat the solvent acts, at least in part, as a plasticizer within (orplasticizes) the electrochromic layer. The solvent, with someembodiments, is present in the electrochromic layer in an amount of from10 to 75 percent by weight, or from 20 to 60 percent by weight, thepercent weights in each case being based on the total weight of theelectrochromic layer and the solvent.

The electrochromic layer, of the electrochromic devices of the presentinvention, includes a polymer matrix. The polymer matrix includes atleast one polymer. The polymer matrix, with some embodiments, is agelled polymer matrix, a crosslinked polymer matrix, and/or athermoplastic polymer matrix.

With some embodiments, the polymer matrix includes a polymer, where thepolymer includes at least one of poly((meth)acrylonitrile),poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linearor branched C₁-C₆ alkylene)), or poly((linear or branched C₁-C₈alkyl)(meth)acrylate).

The polymer matrix, with some embodiments, is present in theelectrochromic layer in an amount of from 5 percent by weight to 80percent by weight, or from 10 percent by weight to 60 percent by weight,or from 15 percent by weight to 50 percent by weight, the percentweights in each case being based on the total weight of theelectrochromic layer.

The electrochromic layer of the electrochromic devices of the presentinvention can, with some embodiments, further include one or moreart-recognized optional additives, such as, but not limited to, thermalstabilizers, UV stabilizers, rheology modifiers, static coloring agents(such as static tints and/or static dyes), kinetic additives (thataccelerate electrode reaction) and combinations thereof. A non-limitingclass of art-recognized thermal stabilizers are phenols, such as2,6-ditertiarybutylphenol and compounds including2,6-ditertiarybutylphenol groups or moieties. A non-limiting class ofart-recognized UV stabilizers are hindered amine light stabilizers(HALS), such as 2,2,6,6-tetramethylpiperidine and compounds including2,2,6,6-tetramehtylpiperidine groups or moieties. Static coloring agentsinclude coloring agents for which the absorption spectrum thereof doesnot change in response to actinic radiation (such as UV and/or visiblelight) or the application of an electric potential, and do not includephotochromic compounds and electrochromic compounds. A non-limitingclass of kinetic additives includes salts, such as: alkali and alkalineearth metal salts of perchlorates, tetrafluoroborates, andhexafluorophosphates; and tetralkylammonium salts. Non-limiting examplesof rheology modifies include: dialkoxyacetophenones, such as3′,4′dimethoxyacetophenone; and optionally substitutedcycloalkylarylketones, such as 1-hydroxycyclohexyl phenyl ketone. Eachoptional additive can be present in any suitable active amount, such asfrom 0.05 percent by weight to 5 percent by weight, based on the totalsolids weight of the electrochromic layer (including the weight of theoptional additive(s)).

The electrochromic layer of the electrochromic devices of the presentinvention can have any suitable thickness. With some embodiments, theelectrochromic layer has a thickness of from 50 micrometers to 800micrometers.

For purposes of non-limiting illustration, an electrochromic device (3)according to the present invention is depicted in FIG. 1 .Electrochromic device (3) includes a first substrate (11) having a firstsurface (14) and a second surface (17). First surface (14) of firstsubstrate (11) includes a first transparent electrode layer (20), whichis electrically conductive. First transparent electrode layer (20)resides over at least a portion of first surface (14) of first substrate(11). With some embodiments, first transparent electrode layer (20) isin the form of one or more patterns (such as, one or more designs and/orindicia) over first surface (14) of first substrate (11). With somefurther embodiments, first transparent electrode layer (20) forms asubstantially continuous layer over first surface (14) of firstsubstrate (11). First transparent electrode layer (20) is, with someembodiments, in electrical contact with at least one first electricalconductor (21), which can be a first electrically conductive wire.

Electrochromic device (3) includes a second substrate (23) having afirst surface (26) and a second surface (29). First surface (26) ofsecond substrate (23) includes a second transparent electrode layer(32), which is electrically conductive. Second transparent electrodelayer (32) resides over at least a portion of first surface (26) ofsecond substrate (23). With some embodiments, second transparentelectrode layer (32) is in the form of one or more patterns (such as,one or more designs and/or indicia) over first surface (26) of secondsubstrate (23). With some further embodiments, second transparentelectrode layer (32) forms a substantially continuous layer over firstsurface (26) of second substrate (23). Second transparent electrodelayer (32) is, with some embodiments, in electrical contact with atleast one second electrical conductor (33), which can be a secondelectrically conductive second wire.

With further reference to electrochromic device (3) of FIG. 1 , firsttransparent electrode layer (20) and second transparent electrode layer(32) are in opposing spaced facing opposition relative to each other.

Electrochromic device (3) further includes an electrochromic layer (35)that is interposed between first transparent electrode layer (20) andsecond transparent electrode layer (32). With some embodiments,electrochromic layer (35) is interposed between and in abuttingrelationship with first transparent electrode layer (20) and secondtransparent electrode layer (32).

The first substrate and the second substrate of the electrochromicdevices are, with some embodiments of the present invention, eachindependently selected from transparent substrates. Transparentsubstrates, from which the first and second substrates can each beindependently selected, are with some embodiments, fabricated frommaterials including, but not limited to, silica glass, organic polymers(such as, but not limited to, polycarbonate polymers), and combinationsthereof. With some embodiments, the transparent substrates, from whichthe first and second substrates can each be independently selected, arefabricated from materials including silica glass. The first and secondsubstrates can each independently have any suitable thickness. With someembodiments, the first and second substrates each independently have athickness of from 1 mm to 25 mm, or from 2 mm to 10 mm.

The first and second transparent electrode layers of the electrochromicdevices of the present invention, with some embodiments, includeelectrically conductive inorganic oxides, electrically conductiveorganic materials, electrically conductive metals, and/or electricallyconductive carbon, such as carbon nanotubes and/or graphene. Examples ofelectrically conductive inorganic oxides, include, but are not limitedto: tin oxide, which can be doped with a doping material, such asindium; and zinc oxide, which can further include, for example,aluminum. Examples of electrically conductive organic materials include,but are not limited to, poly(3,4-ethylenedioxythiophene),poly(4,4-dioctyl cyclopentadithiophene), andpoly(3,4-ethylenedioxythiophene):poly(styrene sulfonate). The first andsecond transparent electrode layers, with some embodiments, can eachindependently be in the form of a grid of metal wires, a grid of carbonnanotubes, and/or a layer of graphene. With some embodiments, the firstand second transparent electrode layers are each independently selectedfrom semi-transparent metal layers. With some further embodiments, oneof the first and second transparent electrode layers includes (or hasassociated therewith) a reflective metal layer (including, for example,aluminum, gold, and/or silver) and the electrochromic device is areflective electrochromic device, such as a controllably reflectivemirror.

In accordance with some embodiments, the first and second electrodelayers of the electrochromic devices of the present invention, eachindependently include an electrically conductive material selected fromindium-tin-oxide, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), or combinations thereof.

The first and second electrode layers of the electrochromic devices, inaccordance with some embodiments of the present invention, can eachindependently have any suitable thickness, provided they are bothtransparent and electrically conductive. With some embodiments, thefirst and second electrode layers of the electrochromic devices of thepresent invention, each independently have a thickness of from 0.01micrometers to 10 micrometers.

Examples of articles, such as articles of manufacture, that may includeor be defined by the electrochromic devices of the present inventioninclude, but are not limited to: energy efficient and/or privacytransparencies (or windows), such as architectural and transportationtransparencies or windows; mirrors, such as rearview mirrors; opticalfilters; and ophthalmic articles, such as corrective lenses,non-corrective lenses, magnifying lenses, protective lenses, and visors;and any other article or application where variable and controllablelight transmission and/or color is desired.

The present invention also relates to an electrochromic composition thatincludes: (i) a cathodic component; (ii) an anodic component includingan anodic component anion selected from at least one anodic componentanion represented by Formula (I) or Formula (II), as describedpreviously herein; (iii) an optional electrolyte; (iv) a polymericthickener; and (v) a solvent.

The cathodic component, the anodic component including an anodiccomponent anion selected from at least one anodic component anionrepresented by Formula (I) or Formula (II), and the optional electrolyteare each as described previously herein with regard to theelectrochromic layer of the electrochromic device of the presentinvention.

The cathodic component, with some embodiments, is present in theelectrochromic composition in an amount of from 0.25 percent by weightto 6.25 percent by weight, or from 0.5 percent by weight to 5 percent byweight, or from 1 percent by weight to 3 percent by weight, the percentweights in each case being based on the total weight of theelectrochromic composition.

The anodic component anion is present in the electrochromic composition,with some embodiments, in an amount of from 0.25 percent by weight to6.25 percent by weight, or from 0.5 percent by weight to 5 percent byweight, or from 1 percent by weight to 3 percent by weight, the percentweights in each case being based on the total weight of theelectrochromic composition.

In accordance with some embodiments, in addition to the anodic componentanion having an anion covalently bonded thereto, such as represented byFormula (I) and/or Formula (II), the anodic component of theelectrochromic composition includes one or more further anodicelectrochromic compounds, such as, but not limited to: ferrocene and/orferrocene derivatives (in which at least one cyclopentadienyl ringthereof is substituted with at least one substituent, including thosesubstituents recited previously herein); 5,10-dihydro-5,10-di(linear orbranched C₁-C₁₀ alkyl)phenazine, such as5,10-dihydro-5,10-dimethylphenazine; N-substitutedphenoxazine, such asN-phenylphenoxazine; and combinations thereof. With some embodiments,the further anodic electrochromic component is present in an amount of 1percent by weight to 50 percent by weight, of from 1 percent by weightto 25 percent by weight, or from 1 percent by weight to 10 percent byweight, or from 1 percent by weight to 5 percent by weight, the percentweights each being based on the total weight of the anodic componentanion and the further anodic electrochromic component. In accordancewith some embodiments, when a further anodic component in present (inaddition to the anodic component anion having an anion covalently bondedthereto) a further cathodic component (or further appropriate amount ofcathodic component) can also be present. The further cathodic component,with some embodiments, comprises one or more cathodic componentsrepresented by Formulas (III) and/or (IV).

The electrolyte is present in the electrochromic composition, with someembodiments, in an amount of from 1 percent by weight to 75 percent byweight, or from 5 percent by weight to 50 percent by weight, or from 10percent by weight to 30 percent by weight, the percent weights in eachcase being based on the total weight of the electrochromic composition.

The polymeric thickener of the electrochromic composition of theelectrochromic composition includes, with some embodiments, a polymer,where the polymer includes at least one of poly((meth)acrylonitrile),poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linearor branched C₁-C₆ alkylene)), or poly((linear or branched C₁-C₈alkyl)(meth)acrylate).

The polymeric thickener is present in the electrochromic composition,with some embodiments, in an amount of from 5 percent by weight to 80percent by weight, or from 10 percent by weight to 60 percent by weight,or from 15 percent by weight to 50 percent by weight, the percentweights in each case being based on the total weight of theelectrochromic composition.

The electrochromic composition of the present invention includes asolvent. With some embodiments, the solvent of the electrochromiccomposition includes at least one of ethylene carbonate, propylenecarbonate, gamma-butyrolactone, gamma-valerolactone,N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters ofpolyethylene glycol, sulfolane, alpha, omega-(C₂-C₈)dinitriles, ordi(linear or branched C₁-C₈)acetamides.

The solvent is present in the electrochromic composition, with someembodiments, in and amount of from 10 to 75 percent by weight, or from20 to 60 percent by weight, or from 25 percent by weight to 50 percentby weight, the percent weights in each case being based on the totalweight of the electrochromic composition.

In accordance with some embodiments, the anodic component, whichincludes the anodic component anion, further includes a counter-cation.Classes and examples of cations from which each counter-cation can beindependently selected from those classes and examples a recitedpreviously herein with regard to the electrochromic device. With someembodiments of the electrochromic composition of the present invention,each counter-cation is independently selected from tetra(linear orbranched alkyl) ammonium cation. In accordance with some furtherembodiments, each counter-cation is independently selected fromtetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.

With some embodiments, the cathodic component of the electrochromiccomposition further includes counter-anions, wherein each counter-anionof the cathodic component is selected from the group consisting of BF₆⁻, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, and B(phenyl)₄ ⁻. Withsome embodiments, the counter-anions of the cathodic component of theelectrochromic composition do not include and are not selected fromanodic component anions, such as represented by Formulas (I) and (II).

The electrochromic composition of the present invention can, with someembodiments, include one or more art-recognized optional additives, suchas, but not limited to, thermal stabilizers, UV stabilizers, rheologymodifiers, static coloring agents (such as static tints and/or staticdyes), kinetic additives (that accelerate electrode reaction) andcombinations thereof. The optional additives are in each case asdescribed previously herein with regard to the electrochromic device ofthe present invention. Each optional additive can be present in theelectrochromic composition in any suitable active amount, such as from0.05 percent by weight to 5 percent by weight, based on the total weightof the electrochromic composition (including the weight of the optionaladditive(s)).

In accordance with some embodiments of the present invention, theelectrochromic layer of the electrochromic device is formed from theelectrochromic composition of the present invention. In accordance withsome embodiments of the present invention, formation of theelectrochromic composition and electrochromic layer includes thefollowing steps. First, all components of the electrochromiccomposition, other than the polymeric thickener, are mixed under sheer(such as with an impeller) until a homogenous mixture is formed.Secondly, the polymeric thickener is added, and the combination issubjected to homogenization, which results in the formation of a thickslurry. A liquid film of the thick slurry is formed, such as using adoctor blade or draw-down bar, on a sacrificial or temporary liner(composed of polyethylene terephthalate, in some embodiments). Theliquid film while on the sacrificial/temporary liner is subjected toelevated temperature, such as from 60° to 90° C. for 3 to 10 minutes,which results in the formation of a solidified film/layer, which is theelectrochromic layer. The solidified film/electrochromic layer, isseparated from the sacrificial/temporary liner (which is discarded), cutto size (if necessary), and placed over or onto a first transparentelectrode layer of a first substrate. The second transparent electrodeof a second substrate is positioned over or onto the other (orfacing/exposed) side of the electrochromic layer, to form a stack thatincludes the first substrate, the first transparent electrode, theelectrochromic layer, the second transparent electrode, and the secondsubstrate. The stack may further include electrical connectors that arein separate electrical contact with the first and second transparentelectrodes. The stack (with an optional gasket surrounding the outeredges of at least the electrochromic layer) is subjected to vacuumlamination, with the concurrent application of elevated temperature,such as from 110° C. to 200° C., for a period of time, such as from 10to 30 minutes. After cooling, the so formed electrochromic device isremoved from vacuum lamination device.

In accordance with the present invention there is also provided acompound represented by Formula (IIa) as described previously herein.The R² divalent linking group and R³ group of Formula (IIa) are each asdescribed previously herein with regard to Formula (II) of theelectrochromic device of the present invention.

With some embodiments, R² of Formula (IIa) is selected from divalentlinear or branched C₁-C₁₀ alkane linking group; and R₃ of Formula (IIa)is selected from fluorine, linear or branched C₁-C₁₀ fluorinated alkyl,or linear or branched C₁-C₁₀ perfluorinated alkyl.

With some further embodiments, R² of Formula (IIa) is selected fromdivalent linear or branched C₁-C₅ alkane linking group; and R³ ofFormula (IIa) is selected from linear or branched C₁-C₅ perfluorinatedalkyl.

The compound represented by Formula (IIa) can be prepared, with someembodiments, by reacting a salt, such as a sodium (Na⁺) or potassium(K⁺) salt, of an anion represented by Formula (II) with a strong acid,such as, but not limited to, HCl, sulfuric acid (H₂SO₄), andbistriflimidic acid, followed by art-recognized purification, isolation,and work-up procedures.

In accordance with the present invention there is further provided asalt including an anion represented by Formula (II) as describedpreviously herein. The R² divalent linking group and R³ group, of thesalt according to the present invention that includes an anionrepresented by Formula (II), are each as described previously hereinwith regard to Formula (II) of the electrochromic device of the presentinvention.

With some embodiments, R² of Formula (II), of the salt according to thepresent invention, is selected from divalent linear or branched C₁-C₁₀alkane linking group; and R³ of Formula (II), of the salt of the presentinvention, is selected from fluorine, linear or branched C₁-C₁₀fluorinated alkyl, or linear or branched C₁-C₁₀ perfluorinated alkyl.

With some further embodiments, R² of Formula (II), of the salt of thepresent invention, is selected from divalent linear or branched C₁-C₅alkane linking group; and R³ of Formula (II), of the salt of the presentinvention, is selected from linear or branched C₁-C₅ perfluorinatedalkyl.

In accordance with some embodiments, the salt of the present inventionincludes: an anion represented by Formula (II); and a counter-cation.With some embodiments of the salt of the present invention, the numberof anions and counter-cations are equivalent, and correspondingly thesalt has a neutral charge. The counter-cation of the salt according tothe present invention is, with some embodiments, as described previouslyherein with regard to the counter-cation of the anodic component of thepresent invention, such as, but not limited to, with reference toFormula (B).

With some embodiments, the counter-cation of the salt according to thepresent invention is selected from tetra(linear or branched alkyl)ammonium cation. With some further embodiments, the counter-cation ofthe salt according to the present invention is selected fromtetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.

The salt of the present invention can have any suitable form, such as asolid form, or in the form of an ionic liquid. With some embodiments,the salt of the present invention is present in a liquid mixture thatfurther includes a solvent, such as water and/or an organic solvent. Theorganic solvent can be selected from any suitable organic solvent, suchas, but not limited to, ethylene carbonate, propylene carbonate,gamma-butyrolactone, gamma-valerolactone, N-methylpyrrolidone,polyethylene glycol, carboxylic acid esters of polyethylene glycol,sulfolane, alpha, omega-(C₂-C₈)dinitriles, or di(linear or branchedC₁-C₈)acetamides.

The present invention can further be characterized by one or more of thefollowing non-limiting clauses.

Clause 1: An electrochromic device comprising:

-   -   (a) a first substrate having a surface comprising a first        transparent electrode layer;    -   (b) a second substrate having a surface comprising a second        transparent conductive electrode layer,        -   wherein said first transparent electrode layer and said            second transparent electrode layer are in opposing spaced            opposition; and    -   (c) an electrochromic layer interposed between said first        transparent electrically conductive electrode layer and said        second transparent electrically conductive electrode layer,        wherein said electrochromic layer comprises,        -   (i) a cathodic component,        -   (ii) an anodic component comprising an anodic component            anion selected from at least one anodic component anion            represented by the following Formula (I) or Formula (II),

-   -   wherein for Formula (I), R¹ is selected from divalent linear or        branched alkane linking group, and    -   wherein for Formula (II), R² is selected from divalent linear or        branched alkane linking group, and R³ is selected from fluorine,        linear or branched fluorinated alkyl, or linear or branched        perfluorinated alkyl,        -   (iii) an optional electrolyte, and        -   (iv) a polymer matrix.

Clause 2: The electrochromic device of clause 1, wherein for Formula(I), R¹ is selected from divalent linear or branched C₁-C₁₀ alkanelinking group, and

-   -   wherein for Formula (II), R² is selected from divalent linear or        branched C₁-C₁₀ alkane linking group; and R³ is selected from        fluorine, linear or branched C₁-C₁₀ fluorinated alkyl, or linear        or branched C₁-C₁₀ perfluorinated alkyl.

Clause 3: The electrochromic device of clause 1 or clause 2, wherein forFormula (I), R¹ is selected from divalent linear or branched C₁-C₅alkyl, and

wherein for Formula (II), R² is selected from divalent linear orbranched C₁-C₅ alkane linking group; and R³ is selected from linear orbranched C₁-C₅ perfluorinated alkyl.

Clause 4: The electrochromic device of clause 1, wherein said anodiccomponent further comprises a counter-cation.

Clause 5: The electrochromic device of clause 4, wherein eachcounter-cation is independently selected from optionally substitutednitrogen-containing aliphatic heterocycle ammonium cations, optionallysubstituted nitrogen-containing aromatic heterocycle ammonium cations,tetrasubstituted ammonium cations, or combinations thereof.

Clause 6: The electrochromic device of clause 4 or clause 5, whereineach counter-cation is independently selected from tetrasubstitutedammonium cations represented by the following Formula (B),

wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom linear or branched alkyl, unsubstituted cycloalkyl, substitutedcycloalkyl, unsubstituted aryl, and substituted aryl.

Clause 7: The electrochromic device of clause 6, wherein R^(a), R^(b),R^(c), and R^(d) are each independently selected from linear or branchedC₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl, substituted C₃-C₇cycloalkyl, unsubstituted phenyl, or substituted phenyl.

Clause 8: The electrochromic device of clause 6 or clause 7, whereinR^(a), R^(b), R^(c), and R^(d) are each independently selected fromlinear or branched C₁-C₁₀ alkyl.

Clause 9: The electrochromic device of any one of clauses 4, 5, 6, 7, or8, wherein each counter-cation is independently selected fromtetra(linear or branched alkyl) ammonium cation.

Clause 10: The electrochromic device of any one of clauses 4, 5, 6, 7,8, or 9, wherein each counter-cation is independently selected fromtetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.

Clause 11: The electrochromic device of any one of clauses 1, 2, 3, 4,5, 6, 7, 8, 9, or 10, wherein said cathodic component comprises at leastone of a 1,1′-disubstituted-4,4′-dipyridinium cation represented by thefollowing Formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented bythe following Formula (VI),

-   -   wherein for Formula (III), R⁴ and R⁵ are each independently        selected from linear or branched C₁-C₁₀ alkyl, unsubstituted        C₃-C₇ cycloalkyl, substituted C₃-C₇ cyloalkyl, unsubstituted        aryl, and substituted aryl, and    -   wherein for Formula (IV), R⁶ and R⁸ are each independently        selected from linear or branched C₁-C₁₀ alkyl, unsubstituted        C₃-C₇ cycloalkyl, substituted C₃-C₇ cyloalkyl, unsubstituted        aryl, and substituted aryl, and R⁷ is selected from divalent        linear or branched C₁-C₁₀ alkane linking group.

Clause 12: The electrochromic device of clause 11, wherein for Formula(III), R⁴ and R⁵ are each independently selected from linear or branchedC₁-C₄ alkyl, unsubstituted phenyl, and substituted phenyl, and

wherein for Formula (IV), R⁶ and R⁸ are each independently selected fromlinear or branched C₁-C₄ alkyl, unsubstituted phenyl, and substitutedphenyl, and R⁷ is selected from divalent linear or branched C₁-C₈ alkanelinking group.

Clause 13: The electrochromic device of any one of clauses 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, and 12, wherein said cathodic component furthercomprises counter-anions, wherein each counter-anion of the cathodiccomponent is selected from the group consisting of BF₄ ⁻, PF₆ ⁻, ClO₄ ⁻,CF₃SO₃, (CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, and B(phenyl)₄ ⁻.

Clause 14: The electrochromic device of any one of clauses 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, or 13, wherein said electrolyte is presentand comprises,

-   -   at least one electrolyte anion, wherein each electrolyte anion        is independently selected from bis(perfluoro(linear or branched        C₁-C₆ alkysulfonyl)imide, and        -   at least one electrolyte cation, wherein each electrolyte            cation is independently selected from 1-(linear or branched            C₁-C₆ alkyl)-3-(linear or branched C₁-C₆ alkyl)imidazolium,            1-(linear or branched C₁-C₆ alkyl)-1-(linear or branched            C₁-C₆ alkyl)piperidinium, or phosphonium cations, such as,            but not limited to tetra(linear or branched C₁-C₆            alkyl)phosphonium, or tri(C₅-C₈ cycloalkyl)-(linear or            branched C₁-C₆ alkyl)phosphonium, or ammonium cations, such            as, but not limited to, tetra(linear or branched            C₁-C₆)ammonium, and tri(C₅-C₈ cycloalkyl)-(linear or            branched C₁-C₆ alkyl)ammonium.

Clause 15: The electrochromic device of any one of clauses 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 wherein said polymer matrixcomprises a polymer, wherein said polymer comprises at least one ofpoly((meth)acrylonitrile), poly(vinylidene fluoride), poly(vinylidenefluoride-co-perfluoro(linear or branched C₁-C₆ alkylene)), orpoly((linear or branched C₁-C₈ alkyl)(meth)acrylate).

Clause 16: An article of manufacture comprising said electrochromicdevice of any one of clauses 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, or 15 wherein said article of manufacture is selected from, energyefficient transparencies, privacy transparencies, mirrors, opticalfilters, or ophthalmic articles.

Clause 17: An electrochromic composition comprising,

-   -   (i) a cathodic component,    -   (ii) an anodic component comprising an anodic component anion        selected from at least one anodic component anion represented by        the following Formula (I) or Formula (II),

-   -   wherein for Formula (I), R¹ is selected from divalent linear or        branched alkane linking group, and    -   wherein for Formula (II), R² is selected from divalent linear or        branched alkane linking group, and R³ is selected from fluorine,        linear or branched fluorinated alkyl, or linear or branched        perfluorinated alkyl,        -   (iii) an optional electrolyte,        -   (iv) a polymeric thickener; and        -   (v) a solvent.

Clause 18: The electrochromic composition of clause 17, wherein forFormula (I), R¹ is selected from divalent linear or branched C₁-C₁₀alkane linking group, and

wherein for Formula (II), R² is selected from divalent linear orbranched C₁-C₁₀ alkane linking group; and R³ is selected from fluorine,linear or branched C₁-C₁₀ fluorinated alkyl, or linear or branchedC₁-C₁₀ perfluorinated alkyl.

Clause 19: The electrochromic composition of clause 17 or clause 18, forFormula (I), R¹ is selected from divalent linear or branched C₁-C₅alkyl, and wherein for Formula (II), R² is selected from divalent linearor branched C₁-C₅ alkane linking group; and R³ is selected from linearor branched C₁-C₅ perfluorinated alkyl.

Clause 20: The electrochromic composition of any one of clauses 17, 18,or 19, wherein said anodic component further comprises a counter-cation.

Clause 21: The electrochromic composition of clause 20, wherein eachcounter-cation is independently selected from optionally substitutednitrogen-containing aliphatic heterocycle ammonium cations, optionallysubstituted nitrogen-containing aromatic heterocycle ammonium cations,tetrasubstituted ammonium cations, or combinations thereof.

Clause 22: The electrochromic composition of clause 20 or clause 21,wherein each counter-cation is selected from tetrasubstituted ammoniumcations represented by the following Formula (B),

wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom linear or branched alkyl, unsubstituted cycloalkyl, substitutedcycloalkyl, unsubstituted aryl, and substituted aryl.

Clause 23: The electrochromic composition of clause 22, wherein R^(a),R^(b), R^(c), and R^(d) are each independently selected from linear orbranched C₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl, substituted C₃-C₇cycloalkyl, unsubstituted phenyl, or substituted phenyl.

Clause 24: The electrochromic composition of clause 22 or clause 23,wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom linear or branched C₁-C₁₀ alkyl.

Clause 25: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, or 24, wherein each counter-cation is independentlyselected from tetra(linear or branched alkyl) ammonium cation.

Clause 26: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, or 25, wherein each counter-cation isindependently selected from tetra(linear or branched C₁-C₁₀ alkyl)ammonium cation.

Clause 27: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, 25, or 26, wherein said cathodic componentcomprises at least one of a 1,1′-disubstituted-4,4′-dipyridinium cationrepresented by the following Formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented bythe following Formula (VI),

-   -   wherein for Formula (III), R⁴ and R⁵ are each independently        selected from linear or branched C₁-C₁₀ alkyl, unsubstituted        C₃-C₇ cycloalkyl, substituted C₃-C₇ cyloalkyl, unsubstituted        aryl, and substituted aryl, and    -   wherein for Formula (IV), R⁶ and R⁸ are each independently        selected from linear or branched C₁-C₁₀ alkyl, unsubstituted        C₃-C₇ cycloalkyl, substituted C₃-C₇ cyloalkyl, unsubstituted        aryl, and substituted aryl, and R⁷ is selected from divalent        linear or branched C₁-C₁₀ alkane linking group.

Clause 28: The electrochromic composition of clause 27, wherein forFormula (III), R⁴ and R⁵ are each independently selected from linear orbranched C₁-C₄ alkyl, unsubstituted phenyl, and substituted phenyl, and

-   -   wherein for Formula (IV), R⁶ and R⁸ are each independently        selected from linear or branched C₁-C₄ alkyl, unsubstituted        phenyl, and substituted phenyl, and R⁷ is selected from divalent        linear or branched C₁-C₈ alkane linking group.

Clause 29: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, or 28, wherein said cathodiccomponent further comprises counter-anions, wherein each counter-anionof the cathodic component is selected from the group consisting of BF₄⁻, PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, and B(phenyl)₄ ⁻.

Clause 30: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29, wherein said electrolyteis present and comprises,

-   -   at least one electrolyte anion, wherein each electrolyte anion        is independently selected from bis(perfluoro(linear or branched        C₁-C₆ alkysulfonyl)imide, and        -   at least one electrolyte cation, wherein each electrolyte            cation is independently selected from 1-(linear or branched            C₁-C₆ alkyl)-3-(linear or branched C₁-C₆ alkyl)imidazolium,            1-(linear or branched C₁-C₆ alkyl)-1-(linear or branched            C₁-C₆ alkyl)piperidinium, or phosphonium cations, such as,            but not limited to tetra(linear or branched C₁-C₆            alkyl)phosphonium, or tri(C₅-C₈ cycloalkyl)-(linear or            branched C₁-C₆ alkyl)phosphonium, or ammonium cations, such            as, but not limited to, tetra(linear or branched            C₁-C₆)ammonium, and tri(C₅-C₈ cycloalkyl)-(linear or            branched C₁-C₆ alkyl)ammonium.

Clause 31: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, wherein saidpolymeric thickener comprises a polymer, wherein said polymer comprisesat least one of poly((meth)acrylonitrile), poly(vinylidene fluoride),poly(vinylidene fluoride-co-perfluoro(linear or branched C₁-C₆alkylene)), or poly((linear or branched C₁-C₈ alkyl)(meth)acrylate).

Clause 32: The electrochromic composition of any one of clauses 17, 18,19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or 31, wherein saidsolvent comprises at least one of ethylene carbonate, propylenecarbonate, gamma-butyrolactone, gamma-valerolactone,N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters ofpolyethylene glycol, sulfolane, alpha, omega-(C₂-C₈)dinitriles, ordi(linear or branched C₁-C₈)acetamides.

Clause 33: A compound represented by the following Formula (IIa),

wherein R² is selected from divalent linear or branched alkane linkinggroup; and R³ is selected from fluorine, linear or branched fluorinatedalkyl, or linear or branched perfluorinated alkyl.

Clause 34: The compound of clause 33, wherein R² is selected fromdivalent linear or branched C₁-C₁₀ alkane linking group; and R³ isselected from fluorine, linear or branched C₁-C₁₀ fluorinated alkyl, orlinear or branched C₁-C₁₀ perfluorinated alkyl.

Clause 35: The compound of clause 33 or clause 34, wherein R² isselected from divalent linear or branched C₁-C₅ alkane linking group;and R³ is selected from linear or branched C₁-C₅ perfluorinated alkyl.

Clause 36: A salt comprising an anion represented by the followingFormula (II),

wherein R¹ is selected from divalent linear or branched alkane linkinggroup; and R² is selected from fluorine, linear or branched fluorinatedalkyl, or linear or branched perfluorinated alkyl.

Clause 37: The salt of clause 36, wherein for said anion represented byFormula (II), R² is selected from divalent linear or branched C₁-C₁₀alkane linking group, and R³ is selected from fluorine, linear orbranched C₁-C₁₀ fluorinated alkyl, or linear or branched C₁-C₁₀perfluorinated alkyl.

Clause 38: The salt of clause 36 or clause 37, wherein for said anionrepresented by Formula (II), R² is selected from divalent linear orbranched C₁-C₅ alkane linking group; and R³ is selected from linear orbranched C₁-C₅ perfluorinated alkyl.

Clause 39: The salt of any one of clauses 36, 37, or 38, wherein saidsalt further comprises a counter-cation.

Clause 40: The salt of clause 39, wherein each counter-cation isindependently selected from optionally substituted nitrogen-containingaliphatic heterocycle ammonium cations, optionally substitutednitrogen-containing aromatic heterocycle ammonium cations,tetrasubstituted ammonium cations, or combinations thereof.

Clause 41: The salt of clause 39 or clause 40, wherein eachcounter-cation is selected from tetrasubstituted ammonium cationsrepresented by the following Formula (B),

wherein R^(a), R^(b), R^(c), and R^(d) are each independently selectedfrom linear or branched alkyl, unsubstituted cycloalkyl, substitutedcycloalkyl, unsubstituted aryl, and substituted aryl.

Clause 42: The salt of clause 41, wherein R^(a), R^(b), R^(c), and R^(d)are each independently selected from linear or branched C₁-C₁₀ alkyl,unsubstituted C₃-C₇ cycloalkyl, substituted C₃-C₇ cycloalkyl,unsubstituted phenyl, or substituted phenyl.

Clause 43: The salt of clause 41 or clause 42, wherein R^(a), R^(b),R^(c), and R^(d) are each independently selected from linear or branchedC₁-C₁₀ alkyl.

Clause 44: The salt of any one of clauses 36, 37, 38, 39, 40, 41, 42, or43, wherein each counter-cation is independently selected fromtetra(linear or branched alkyl) ammonium cation.

Clause 45: The salt of any one of clauses 36, 37, 38, 39, 40, 41, 42,43, or 44, wherein each counter-cation is independently selected fromtetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.

The present invention is more particularly described in the followingexamples, which are intended as illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLES

In Part-1 of the following examples there is described the synthesis ofanodic component anions of the anodic component, and salts, according tothe present invention.

In Part-2, there is described the preparation of an electrochromicdevice according to the present invention. In Part-3, evaluation of theelectrochromic device of Part-2 is described.

Part-1 Synthesis Example 1

With reference to Scheme-(1) below, there is provided a non-limitingdescription of the preparation of an anodic component anion according tothe present invention represented by Formula (I), where R¹ is a divalentn-propane linking group.

Into an oven dried 3-neck, 500 ml round bottomed flask with magneticstirring was added 200 mL of dimethylformamide (DMF) and 10 g of (1)phenothiazine (50.2 mmol). The solution was stirred while being purgewith nitrogen for 1 hour. To the reaction mixture was added 2.4 g of 60%NaH (60 mmol). The solution was observed to turn deep red as bubbleswere produced therefrom. After continuous mixing under nitrogen for onehour, the production of bubbles was observed to cease. While under anitrogen sweep is 6.6 g of (2) 1,3-propanesultone (55.2 mmol) dissolvedin 10 g of dry DMF, was added drop-wise to the contents of the flask.After completion of the addition of (2) 1,3-propanesultone, the reactionmixture was left to stir at room temperature for 18 hours undernitrogen.

The reaction was quenched by the addition of 100 mL of deionized (DI)water and the solvent was removed by the application of vacuum, afterwhich an oily substance remained in the flask. To the oily substance wasadded 50 mL of ethyl acetate, which resulted in the formation of aprecipitate that was collected by vacuum filtration. The precipitate waswashed with cold ethyl acetate and dried overnight under vacuum at 60°C. to yield the desired product (3) sodium3-(10H-phenothiazin-10-yl)-propane-1-sulfonate, as an off-white solid.

Synthesis Example 2

With reference to Scheme-(2) below, there is provided a non-limitingdescription of the preparation of an anodic component anion according tothe present invention represented by Formula (II), where R² is adivalent n-propane linking group, and R³ is trifluoromethyl.

The (3) sodium 3-(10H-phenothiazin-10-yl)-propane-1-sulfonate wasprepared in accordance with Synthesis Example 1. One gram (0.0029 mol)of (3) sodium 3-(10H-phenothiazin-10-yl)propane-1-sulfonate was fineground with mortar and pestle, and then placed in a 100 ml round-bottomflask equipped with a magnetic stir bar and a reflux condenser with a N₂sweep/blanket. Acetone in an amount of 20 ml and 40 mg of 18-crown-6ether were added to the flask and the mixture was stirred vigorously for15 minutes. The solution turned cloudy, but solid sodium salt (3) wasobserved to be present. (4) Cyanuric chloride (540 mg, 0.0029 mol, 1equiv.) was added under vigorous stirring under N₂. The mixture wasrefluxed for 24 hours on an oil bath (at about 80° C.). The color of thesolution turned orange and a fine precipitate formed. Large chunks ofinitial Na salt (3) were no longer observable. Thin layer chromatography(TLC) showed the presence of a single reaction product that turned pinkupon exposure to short-wave (316 nm) UV in air, evidencing formation of(5) 3-(10H-phenothiazin-10-yl)-propane-1-sulfonyl chloride. The product(5) was fairly mobile in 50:50 EtOAc/Hexanes. The reaction mixture wascooled to room temperature and filtered through a thin layer of alumina.The solvent was removed under vacuum to give 1.25 g of orange-yellowglassy solid (5). The product (5) was dissolved in MeCN and the solidswere filtered off. The filtrate was used in the next step withoutadditional purification.

(6) Trifluoromethylsulfonamide (4.53 g, 0.0305 mol, 1.05 equiv.) andpotassium carbonate (40 g, 0.29 mol, 10 equiv.) were placed in a 500 ml3-neck flask equipped with a reflux condenser, magnetic stir bar and afritted Schlenk funnel. Nitrogen feeds were attached to the condenserand the Schlenk funnel and secured with plastic clips. An intensenitrogen flux was used to flush the vessel for 15 seconds, and a septumwas installed in the remaining neck. Anhydrous MeCN in an amount of 100ml was added through the septum using a syringe. The mixture wasvigorously stirred for 20 minutes, yielding a white hazy dispersion. Tothe crude (5) 3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride(9.84 g, 0.029 mol) (filtrate of the preceding step) was added 50 ml dryMeCN under nitrogen flux, and the resulting solution was moved to thefritted Schlenk funnel. The Schlenk funnel was purged with nitrogen andplugged with a stopper secured with a clip. The solution of MeCN and (5)3-(10H-phenothiazin-10-yl)propane-1-sulfonyl chloride was added dropwiseto the 3-neck flask over a period of one hour at room temperature. Thecontents of the 3-neck flask were refluxed for 24 hours. Formation ofbulky precipitate was observed. The precipitate was filtered off and theresulting solution was concentrated under vacuum. The residue wasrecrystallized from water to yield the product (7) potassium3-(10H-phenothiazin-10-yl)-N-((trifluoromethyl)sulfonyl)propane-1-sulfonamide,in the form of brown needles.

Part-2

An electrochromic device according to the present invention was preparedin accordance with the following procedure. An initial solution wasprepared with magnetic stirring of the following: propylene carbonate (7g); ethylene carbonate (3 g); 1-ethyl-3-methylimidazoliumbis(trifluoromethane)sulfonimide (EMIM-TFSI) (1 g); potassium3-(10H-phenothiazin-10-yl)-N-triflylpropane-1-sulfonamide (PTTK) (100mg); and 1,1′-diethyl-4,4′-bipyridinium bis(trifluoromethane)sulfonimide(diethyl viologen TFSI) (100 mg). To the initial solution was added 3.5g of polyacrylonitrile, followed by homogenization, which resulted inthe formation of a thick slurry. A liquid film of the thick slurry wasformed using a doctor blade on a sacrificial polyethylene terephthalate(PET) liner, to a thickness of 400 micrometers (um). The liquid film washeated to 70° C. for 10 minutes, which resulted in the formation of asolidified film/layer, which was the electrochromic layer. Thesolidified film/electrochromic layer, was separated from thesacrificial/temporary liner, cut to size (2″×3″; 5.08 cm×7.62 cm), andplaced onto a fluorine-doped tin oxide (FTO)-glass electrode (3″×4″;7.62 cm×10.16 cm) that already had copper tape wrapped over the edge,which was covered with insulating polyimide. A prefabricatedthermoplastic gasket of 0.5″ (1.27 cm) in width and 400 microns inthickness was added, which surrounded the active area. A secondfluorine-doped tin oxide (FTO)-glass was positioned over of theelectrochromic layer. The stack was subjected to vacuum lamination at140° C. for 15 minutes to fully melt and seal the gasket. After cooling,the so formed electrochromic device was removed from vacuum laminationdevice.

Part-3

Plots of % Transmission vs. Wavelength (nm) of the electrochromic deviceof Part-2 in the clear/unactivated state and the dark/activated state(in each case at room temperature) are depicted in FIG. 2 of thedrawings. With reference to FIG. 2 , the electrochromic device accordingto the present invention provides a significant and desirable level ofdarkening (i.e., reduced visual light transmission) when activated, ascompared to the clear/unactivated state thereof. In FIG. 2 , theelectrochromic device of Part-2 is described as a “PTTK-EthylViologenDevice.” With additional reference to FIG. 2 : the plot of %Transmission vs. Wavelength in the clear/unactivated state is labeled“PTTK-EV Clear”; and the plot of % Transmission vs. Wavelength in thedarkened/activated state is labeled “PTTK-EV Dark.”

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as to the extent that they are included in theaccompanying claims.

What is claimed is:
 1. An electrochromic device comprising: (a) a firstsubstrate having a surface comprising a first transparent electrodelayer; (b) a second substrate having a surface comprising a secondtransparent conductive electrode layer, wherein said first transparentelectrode layer and said second transparent electrode layer are inopposing spaced opposition; and (c) an electrochromic layer interposedbetween said first transparent electrically conductive electrode layerand said second transparent electrically conductive electrode layer,wherein said electrochromic layer comprises, (i) a cathodic component,(ii) an anodic component comprising an anodic component anion selectedfrom at least one anodic component anion represented by the followingFormula (I) or Formula (II),

wherein for Formula (I), R¹ is selected from divalent linear or branchedalkane linking group, and wherein for Formula (II), R² is selected fromdivalent linear or branched alkane linking group, and R³ is selectedfrom fluorine, linear or branched fluorinated alkyl, or linear orbranched perfluorinated alkyl, (iii) an optional electrolyte, and (iv) apolymer matrix.
 2. The electrochromic device of claim 1, wherein forFormula (I), R¹ is selected from divalent linear or branched C₁-C₁₀alkane linking group, and wherein for Formula (II), R² is selected fromdivalent linear or branched C₁-C₁₀ alkane linking group; and R³ isselected from fluorine, linear or branched C₁-C₁₀ fluorinated alkyl, orlinear or branched C₁-C₁₀ perfluorinated alkyl.
 3. The electrochromicdevice of claim 2, wherein for Formula (I), R¹ is selected from divalentlinear or branched C₁-C₅ alkyl, and wherein for Formula (II), R² isselected from divalent linear or branched C₁-C₅ alkane linking group;and R³ is selected from linear or branched C₁-C₅ perfluorinated alkyl.4. The electrochromic device of claim 1, wherein said anodic componentfurther comprises a counter-cation.
 5. The electrochromic device ofclaim 4, wherein each counter-cation is independently selected fromtetra(linear or branched alkyl) ammonium cation.
 6. The electrochromicdevice of claim 5, wherein each counter-cation is independently selectedfrom tetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.
 7. Theelectrochromic device of claim 1, wherein said cathodic componentcomprises at least one of a 1,1′-disubstituted-4,4′-dipyridinium cationrepresented by the following Formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented bythe following Formula (VI),

wherein for Formula (III), R⁴ and R⁵ are each independently selectedfrom linear or branched C₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl,substituted C₃-C₇ cyloalkyl, unsubstituted aryl, and substituted aryl,and wherein for Formula (IV), R⁶ and R⁸ are each independently selectedfrom linear or branched C₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl,substituted C₃-C₇ cyloalkyl, unsubstituted aryl, and substituted aryl,and R⁷ is selected from divalent linear or branched C₁-C₁₀ alkanelinking group.
 8. The electrochromic device of claim 7, wherein forFormula (III), R⁴ and R⁵ are each independently selected from linear orbranched C₁-C₄ alkyl, unsubstituted phenyl, and substituted phenyl, andwherein for Formula (IV), R⁶ and R⁸ are each independently selected fromlinear or branched C₁-C₄ alkyl, unsubstituted phenyl, and substitutedphenyl, and R⁷ is selected from divalent linear or branched C₁-C₈ alkanelinking group.
 9. The electrochromic device of claim 7, wherein saidcathodic component further comprises counter-anions, wherein eachcounter-anion of the cathodic component is selected from the groupconsisting of BF₄ ⁻, PF⁶⁺, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻,and B(phenyl)₄ ⁻.
 10. The electrochromic device of claim 1, wherein saidelectrolyte is present and comprises, at least one electrolyte anion,wherein each electrolyte anion is independently selected frombis(perfluoro(linear or branched C₁-C₆ alkysulfonyl)imide, and at leastone electrolyte cation, wherein each electrolyte cation is independentlyselected from 1-(linear or branched C₁-C₆ alkyl)-3-(linear or branchedC₁-C₆ alkyl)imidazolium, 1-(linear or branched C₁-C₆ alkyl)-1-(linear orbranched C₁-C₆ alkyl)piperidinium, tetra(linear or branchedC₁-C₆)ammonium, or tri(C₅-C₈ cycloalkyl)-(linear or branched C₁-C₆alkyl)ammonium.
 11. The electrochromic device of claim 1, wherein saidpolymer matrix comprises a polymer, wherein said polymer comprises atleast one of poly((meth)acrylonitrile), poly(vinylidene fluoride),poly(vinylidene fluoride-co-perfluoro(linear or branched C₁-C₆alkylene)), or poly((linear or branched C₁-C₈ alkyl)(meth)acrylate). 12.An electrochromic composition comprising, (i) a cathodic component, (ii)an anodic component comprising an anodic component anion selected fromat least one anodic component anion represented by the following Formula(I) or Formula (II),

wherein for Formula (I), R¹ is selected from divalent linear or branchedalkane linking group, and wherein for Formula (II), R² is selected fromdivalent linear or branched alkane linking group, and R³ is selectedfrom fluorine, linear or branched fluorinated alkyl, or linear orbranched perfluorinated alkyl, (iii) an optional electrolyte, (iv) apolymeric thickener; and (v) a solvent.
 13. The electrochromiccomposition of claim 12, wherein for Formula (I), R¹ is selected fromdivalent linear or branched C₁-C₁₀ alkane linking group, and wherein forFormula (II), R² is selected from divalent linear or branched C₁-C₁₀alkane linking group; and R³ is selected from fluorine, linear orbranched C₁-C₁₀ fluorinated alkyl, or linear or branched C₁-C₁₀perfluorinated alkyl.
 14. The electrochromic composition of claim 13,for Formula (I), R¹ is selected from divalent linear or branched C₁-C₅alkyl, and wherein for Formula (II), R² is selected from divalent linearor branched C₁-C₅ alkane linking group; and R³ is selected from linearor branched C₁-C₅ perfluorinated alkyl.
 15. The electrochromiccomposition of claim 12, wherein said anodic component further comprisesa counter-cation.
 16. The electrochromic composition of claim 15,wherein each counter-cation is independently selected from tetra(linearor branched alkyl) ammonium cation.
 17. The electrochromic compositionof claim 16, wherein each counter-cation is independently selected fromtetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.
 18. Theelectrochromic composition of claim 12, wherein said cathodic componentcomprises at least one of a 1,1′-disubstituted-4,4′-dipyridinium cationrepresented by the following Formula (III), or a 1,1-(alkane-alpha,omega-diyl)-bis-(1′-substituted-4,4′-dipyridinium) cation represented bythe following Formula (VI),

wherein for Formula (III), R⁴ and R⁵ are each independently selectedfrom linear or branched C₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl,substituted C₃-C₇ cyloalkyl, unsubstituted aryl, and substituted aryl,and wherein for Formula (IV), R⁶ and R⁸ are each independently selectedfrom linear or branched C₁-C₁₀ alkyl, unsubstituted C₃-C₇ cycloalkyl,substituted C₃-C₇ cyloalkyl, unsubstituted aryl, and substituted aryl,and R⁷ is selected from divalent linear or branched C₁-C₁₀ alkanelinking group.
 19. The electrochromic composition of claim 18, whereinfor Formula (III), R⁴ and R⁵ are each independently selected from linearor branched C₁-C₄ alkyl, unsubstituted phenyl, and substituted phenyl,and wherein for Formula (IV), R⁶ and R⁸ are each independently selectedfrom linear or branched C₁-C₄ alkyl, unsubstituted phenyl, andsubstituted phenyl, and R⁷ is selected from divalent linear or branchedC₁-C₈ alkane linking group.
 20. The electrochromic composition of claim18, wherein said cathodic component further comprises counter-anions,wherein each counter-anion of the cathodic component is selected fromthe group consisting of BF⁴⁻, PF₆ ⁻, ClO₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻,(CF₃SO₂)₃C⁻, and B(phenyl)₄ ⁻.
 21. The electrochromic composition ofclaim 12, wherein said electrolyte is present and comprises, at leastone electrolyte anion, wherein each electrolyte anion is independentlyselected from bis(perfluoro(linear or branched C₁-C₆ alkysulfonyl)imide,and at least one electrolyte cation, wherein each electrolyte cation isindependently selected from 1-(linear or branched C₁-C₆ alkyl)-3-(linearor branched C₁-C₆ alkyl)imidazolium, 1-(linear or branched C₁-C₆alkyl)-1-(linear or branched C₁-C₆ alkyl)piperidinium, tetra(linear orbranched C₁-C₆)ammonium, or tri(C₅-C8 cycloalkyl)-(linear or branchedC₁-C₆ alkyl)ammonium.
 22. The electrochromic composition of claim 12,wherein said polymeric thickener comprises a polymer, wherein saidpolymer comprises at least one of poly((meth)acrylonitrile),poly(vinylidene fluoride), poly(vinylidene fluoride-co-perfluoro(linearor branched C₁-C₆ alkylene)), or poly((linear or branched C₁-C₈alkyl)(meth)acrylate).
 23. The electrochromic composition of claim 12,wherein said solvent comprises at least one of ethylene carbonate,propylene carbonate, gamma-butyrolactone, gamma-valerolactone,N-methylpyrrolidone, polyethylene glycol, carboxylic acid esters ofpolyethylene glycol, sulfolane, alpha, omega-(C₂-C₈)dinitriles, ordi(linear or branched C₁-C₈)acetamides.
 24. A compound represented bythe following Formula (IIa),

wherein R² is selected from divalent linear or branched alkane linkinggroup; and R³ is selected from fluorine, linear or branched fluorinatedalkyl, or linear or branched perfluorinated alkyl.
 25. The compound ofclaim 24, wherein R² is selected from divalent linear or branched C₁-C₁₀alkane linking group; and R³ is selected from fluorine, linear orbranched C₁-C₁₀ fluorinated alkyl, or linear or branched C₁-C₁₀perfluorinated alkyl.
 26. The compound of claim 25, wherein R² isselected from divalent linear or branched C₁-C₅ alkane linking group;and R³ is selected from linear or branched C₁-C₅ perfluorinated alkyl.27. A salt comprising an anion represented by the following Formula(II),

wherein R¹ is selected from divalent linear or branched alkane linkinggroup; and R² is selected from fluorine, linear or branched fluorinatedalkyl, or linear or branched perfluorinated alkyl.
 28. The salt of claim27, wherein for said anion represented by Formula (II), R² is selectedfrom divalent linear or branched C₁-C₁₀ alkane linking group, and R³ isselected from fluorine, linear or branched C₁-C₁₀ fluorinated alkyl, orlinear or branched C₁-C₁₀ perfluorinated alkyl.
 29. The salt of claim28, wherein for said anion represented by Formula (II), R² is selectedfrom divalent linear or branched C₁-C₅ alkane linking group; and R³ isselected from linear or branched C₁-C₅ perfluorinated alkyl.
 30. Thesalt of claim 27, wherein said salt further comprises a counter-cation.31. The salt of claim 30, wherein each counter-cation is independentlyselected from tetra(linear or branched alkyl) ammonium cation.
 32. Thesalt of claim 31, wherein each counter-cation is independently selectedfrom tetra(linear or branched C₁-C₁₀ alkyl) ammonium cation.